Semiconductor deposition reactor manifolds

ABSTRACT

The present disclosure pertains to embodiments of a semiconductor deposition reactor manifold and methods of using the semiconductor deposition reactor manifold which can be used to deposit semiconductor layers using processes such as atomic layer deposition (ALD). The semiconductor deposition reactor manifold has a bore, a first supply channel, and a second supply channel. Advantageously, the first supply channel and the second supply channel merge with the bore in an offset fashion which leads to reduced cross-contamination within the supply channels.

CROSS-REFERENCE TO RELATED APPLICATIONS

Any and all applications for which a foreign or domestic priority claim is identified in the Application Data Sheet as filed with the present application are hereby incorporated by reference under 37 C.F.R. § 1.57.

BACKGROUND Field

The field relates generally to manifolds for vapor deposition, and, in particular, to manifolds for improving the quality of deposition in an atomic layer deposition (ALD) reactor.

Description of the Related Art

There are several vapor deposition methods for depositing thin films on surfaces of substrates. These methods include vacuum evaporation deposition, Molecular Beam Epitaxy (MBE), different variants of Chemical Vapor Deposition (CVD) (including low-pressure and organometallic CVD and plasma-enhanced CVD), and Atomic Layer Deposition (ALD).

In an ALD process, one or more substrates with at least one surface to be coated are introduced into a deposition chamber. The substrate is heated to a desired temperature, typically above the condensation temperatures of the selected vapor phase reactants and below their thermal decomposition temperatures. One reactant is capable of reacting with the adsorbed species of a prior reactant to form a desired product on the substrate surface. Two, three or more reactants are provided to the substrate, typically in spatially and temporally separated pulses.

In an example, in a first pulse, a first reactant representing a precursor material is adsorbed largely intact in a self-limiting process on a wafer. The process is self-limiting because the vapor phase precursor cannot react with or adsorb upon the adsorbed portion of the precursor. After any remaining first reactant is removed from the wafer or chamber, the adsorbed precursor material on the substrate reacted with a subsequent reactant pulse to form no more than a single molecular layer of the desired material. The subsequent reactant may, e.g., strip ligands from the adsorbed precursor material to make the surface reactive again, replace ligands and leave additional material for a compound, etc. In an unadulterated ALD process, less than a monolayer is formed per cycle on average due to steric hindrance, whereby the size of the precursor molecules prevent access to adsorption sites on the substrate, which may become available in subsequent cycles. Thicker films are produced through repeated growth cycles until the target thickness is achieved. Growth rate is often provided in terms of angstroms per cycle because in theory the growth depends solely on number of cycles, and has no dependence upon mass supplied or temperature, as long as each pulse is saturative and the temperature is within the ideal ALD temperature window for those reactants (no thermal decomposition and no condensation).

Reactants and temperatures are typically selected to avoid both condensation and thermal decomposition of the reactants during the process, such that chemical reaction is responsible for growth through multiple cycles. However, in certain variations on ALD processing, conditions can be selected to vary growth rates per cycle, possibly beyond one molecular monolayer per cycle, by utilizing hybrid CVD and ALD reaction mechanisms. Other variations may be allow some amount of spatial and/or temporal overlap between the reactants. In ALD and other sequential vapor deposition variations thereof, two, three, four or more reactants can be supplied in sequence in a single cycle, and the content of different cycles can be varied to tailor composition.

During a typical ALD process, the reactant pulses, all of which are in vapor form, are pulsed sequentially into a reaction space (e.g., reaction chamber) with removal steps between reactant pulses to avoid direct interaction between reactants in the vapor phase. For example, inert gas pulses or “purge” pulses can be provided between the pulses of reactants. The inert gas purges the chamber of one reactant pulse before the next reactant pulse to avoid gas phase mixing. To obtain a self-limiting growth, a sufficient amount of each precursor is provided to saturate the substrate. As the growth rate in each cycle of a true ALD process is self-limiting, the rate of growth is proportional to the repetition rate of the reaction sequences rather than to the flux of reactant.

SUMMARY

In one aspect a semiconductor processing device is provided which includes: a manifold including: a bore configured to deliver vaporized reactant to a reaction chamber, the bore extending along a longitudinal axis; an upper wall disposed at an upper portion of the manifold, the upper wall defining a capping surface at a first end of the bore along the longitudinal axis; an outlet at a lower portion of the manifold along the longitudinal axis, the outlet configured to deliver gas to a reactor; a first supply channel configured to supply gas to the bore; and a second supply channel configured to supply gas to the bore, wherein the first supply channel and the second supply channel merge with the bore at offset positions along the longitudinal axis.

In some embodiments, the capping surface is shaped to redirect upwardly directed gas downwardly back through the bore to the outlet.

In some embodiments, the semiconductor processing device further includes a first block mounted to the manifold, the first block and the manifold cooperating to at least partially define the first supply channel. In some embodiments, the semiconductor processing device further includes a second block mounted to the manifold, the second block and the manifold cooperating to at least partially define the second supply channel.

In some embodiments, the first supply channel is in fluid communication with a first reactant source and is configured to deliver a first vaporized reactant to the bore, and the second supply channel is in fluid communication with a second reactant source and is configured to deliver a second vaporized reactant to the bore.

In some embodiments, the first supply channel is in fluid communication with an inactive gas to purge the bore.

In some embodiments, the semiconductor processing device further includes a showerhead device below the outlet, the showerhead device configured to disperse a flow of the gas from the outlet. The semiconductor processing device can further include a reaction chamber below the showerhead device and a substrate support configured to support a substrate in the reaction chamber.

In some embodiments, the first block includes a first vapor phase inlet configured to input a first reactant into the first supply channel.

In some embodiments, the first block further includes a second vapor phase inlet and a third vapor phase inlet. In some embodiments, the first block further includes a fourth vapor phase inlet, wherein the fourth vapor phase inlet is located on a lateral side of the first block opposite to the manifold.

In some embodiments, the fourth vapor phase inlet is configured to input a purge gas into the manifold.

In some embodiments, the first supply channel is angled towards the capping surface and the second supply channel is angled towards the outlet, the second supply channel downstream of the first supply channel.

In some embodiments, the manifold includes a single monolithic block.

In some embodiments, the bore extends continuously along the longitudinal axis.

In another aspect, a semiconductor processing device is provided which includes: a manifold including a bore configured to deliver gas to a reaction chamber, the bore disposed along a longitudinal axis; an upper wall disposed at an upper portion of the manifold, the upper wall defining a capping surface at a first end of the bore along the longitudinal axis; a first supply line configured to supply an inactive purge gas to the bore at a first location along the longitudinal axis downstream of the capping surface; a second supply line configured to supply a gas to the bore at a second location along the longitudinal axis, the second location different from the first location.

In some embodiments, the supply line is connected to an inactive gas source to purge the bore.

In some embodiments, the inactive gas comprises at least one of argon gas and nitrogen gas.

In another aspect, a method of deposition, is provided. The method includes: supplying a first gas through a first supply channel to a bore of a manifold at a first location along a longitudinal axis of the bore, a capping surface disposed at an upper end of the bore; supplying a second gas through a second supply channel to the bore of the manifold at a second location along the longitudinal axis of the bore that is longitudinally offset from the first supply channel; directing at least one of the first gas and the second gas downstream along the longitudinal axis towards an outlet of the bore.

In some embodiments, supplying the first and second gases comprises supplying a first vaporized reactant and supplying a second vaporized reactant. In some embodiments, the method further includes purging the reaction chamber with an inactive gas after supplying the first vaporized reactant and before supplying the second vaporized reactant. The inactive gas can include at least one of nitrogen gas and argon gas. The first vaporized reactant can include at least one of H₂, NH₃, N₂, O₂, or O. The second vaporized reactant can include at least one of dichlorosilane (DCS), trichlorosilane (TCS), trisilane, organic silanes, titanium chloride (TiCl₄), ZrCl₄, and HfCl₄. The first vaporized reactant can include NH₃ and the second vaporized reactant can include TiCl₄. In some embodiments, the method includes vaporizing liquid TiCl₄ to create the second vaporized reactant.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features, aspects and advantages of the present invention will now be described with reference to the drawings of several embodiments, which embodiments are intended to illustrate and not to limit the invention.

FIG. 1 is a schematic perspective view of an illustrative embodiment of a semiconductor processing device.

FIG. 2 is a schematic side sectional view of a semiconductor processing device having an inactive gas inlet at an upper portion of a manifold body.

FIGS. 3A-C are images of various components of the semiconductor processing device of FIG. 2.

FIG. 4A is an additional cross-sectional view of the semiconductor processing device of FIG. 2.

FIG. 4B is a cross-sectional view of a portion of the semiconductor processing device of FIG. 1.

FIG. 5A is a top down view of the semiconductor processing device of FIG. 2.

FIG. 5B is a top down view of the semiconductor processing device of FIGS. 1 and 4B.

FIG. 6A is a top cross-sectional view of the semiconductor processing device of FIG. 4A.

FIG. 6B is a top cross-sectional view of the semiconductor processing device of FIG. 4B.

FIG. 7A is a perspective view of a bore and supply channels of a semiconductor processing device, according to various embodiments.

FIG. 7B is a perspective view of a bore and supply channels of the semiconductor processing device of FIGS. 4B, 5B, and 6B.

FIGS. 8A and 8B are velocity plots vapors passing through the respective bores for the two different supply channel designs of FIGS. 7A and 7B.

FIGS. 9A and 9B are mole fraction plots of ammonia (NH₃) reactant for the respective bores of the two different supply channel designs of FIGS. 7A and 7B.

FIGS. 10A and 10B are plots of mole fraction of NH₃ reactant at positions within the supply channels and the bore respectively for the two different supply channel designs of FIGS. 7A and 7B.

DETAILED DESCRIPTION

The embodiments disclosed herein can be utilized with semiconductor processing devices configured for any suitable gas or vapor deposition process, including processes that alternate reactant exposures (e.g., pulses) to the substrate. For example, the illustrated embodiments show various systems for depositing material on a substrate using atomic layer deposition (ALD) techniques. Among vapor deposition techniques, ALD has many advantages, including high conformity at low temperatures and fine control of composition during the process. ALD type processes are based on controlled, self-limiting surface reactions of precursor chemicals. Gas phase reactions are avoided by feeding the precursors alternately and sequentially into the reaction chamber. Vapor phase reactants are separated from each other in the reaction chamber, for example, by removing excess reactants and/or reactant by-products from the reaction chamber between reactant pulses. Removal can be accomplished by a variety of techniques, including purging and/or lowering pressure between pulses. Pulses can be sequential in a continuous flow, or the reactor can be isolated and can backfilled for each pulse. Of course, the equipment disclosed herein can be useful for other vapor deposition processes, particularly those in which alternation of reactants is desired, such that processes employed by the equipment may include some degree of thermal decomposition and/or overlap of precursor spatially or temporally.

Briefly, a substrate is loaded into a reaction chamber and is heated to a suitable deposition temperature, generally at lowered pressure. Deposition temperatures are typically maintained below the precursor thermal decomposition temperature but at a high enough level to avoid condensation of reactants and to provide the activation energy for the desired surface reactions. Of course, the appropriate temperature window for any given ALD reaction will depend upon the surface termination and reactant species involved, and processes that allow for either condensation or thermal decomposition can be conducted with equipment described herein.

A first reactant can be conducted into the chamber in the form of a vapor phase pulse and contacted with the surface of a substrate. Any suitable reactant vapor can be pulsed into the chamber. In various embodiments, for example, the first vaporized reactant can comprise ammonia (NH₃). Conditions can be selected such that no more than about one monolayer of the precursor is adsorbed on the substrate surface in a self-limiting manner. Excess first reactant and reaction byproducts, if any, are purged from the reaction chamber, often with a pulse of inert gas such as nitrogen or argon.

Purging the reaction chamber means that vapor phase precursors and/or vapor phase byproducts are removed from the reaction chamber such as by evacuating the chamber with a vacuum pump and/or by replacing the gas inside the reactor with an inert gas such as argon or nitrogen. Typical purging times for a single wafer reactor are from about 0.05 to 20 seconds, particularly between about 1 and 10 seconds, and still more particularly between about 1 and 2 seconds. However, other purge times can be utilized if desired, such as when depositing layers over extremely high aspect ratio structures or other structures with complex surface morphology is needed, or when a high volume batch reactor is employed. The appropriate pulsing times can be readily determined by the skilled artisan based on the particular circumstances.

A second gaseous reactant can be pulsed into the chamber where it reacts with the first reactant bound to the surface. Any suitable reactant vapor can be pulsed into the chamber. In various embodiments, for example, the second vaporized reactant can comprise titanium chloride, or TiCl₄. Excess second reactant and gaseous by-products of the surface reaction are purged out of the reaction chamber, preferably with the aid of an inert gas. The steps of pulsing and purging are repeated until a thin film of the desired thickness has been formed on the substrate, with each cycle leaving no more than a molecular monolayer. Some ALD processes can have more complex sequences with three or more precursor pulses alternated, where each precursor contributes elements to the growing film. Reactants can also be supplied in their own pulses or with precursor pulses to strip or getter adhered ligands and/or free by-product, rather than contribute elements to the film. Additionally, not all cycles need to be identical. For example, a binary film can be doped with a third element by infrequent addition of a third reactant pulse, e.g., every fifth cycle, in order to control stoichiometry of the film, and the frequency can change during the deposition in order to grade film composition. Moreover, while described as starting with an adsorbing reactant, some recipes may start with the other reactant or with a separate surface treatment, for example to ensure maximal reaction sites to initiate the ALD reactions (e.g., for certain recipes, a water pulse can provide hydroxyl groups on the substrate to enhance reactivity for certain ALD precursors).

As mentioned above, each pulse or phase of each cycle is preferably self-limiting for ALD reactions. An excess of reactant precursors is supplied in each phase to saturate the susceptible structure surfaces. Surface saturation ensures reactant occupation of all available reactive sites (subject, for example, to physical size or steric hindrance restraints) and thus ensures excellent step coverage over any topography on the substrate. In some arrangements, the degree of self-limiting behavior can be adjusted by, e.g., allowing some overlap of reactant pulses to trade off deposition speed (by allowing some CVD-type reactions) against conformity. Ideal ALD conditions with reactants well separated in time and space provide near perfect self-limiting behavior and thus maximum conformity, but steric hindrance results in less than one molecular layer per cycle. Limited CVD reactions mixed with the self-limiting ALD reactions can raise the deposition speed. While embodiments described herein are particularly advantageous for sequentially pulsed deposition techniques, like ALD and mixed-mode ALD/CVD, the manifold can also be employed for pulsed or continuous CVD processing. Many kinds of reactors capable of ALD growth of thin films, including CVD reactors equipped with appropriate equipment and means for pulsing the precursors, can be employed. In some embodiments a flow type ALD reactor is used, as compared to a backfilled reactor. In some embodiments, the manifold is upstream of an injector designed to distribute gas into the reaction space, particularly a dispersion mechanism such as a showerhead assembly above a single-wafer reaction space.

The ALD processes can optionally be carried out in a reaction chamber or space connected to a cluster tool. In a cluster tool, because each reaction space is dedicated to one type of process, the temperature of the reaction space in each module can be kept constant, which improves the throughput compared to a reactor in which the substrate is heated to the process temperature before each run. A stand-alone reactor can be equipped with a load-lock. In that case, it is not necessary to cool down the reaction chamber or space between each run. These processes can also be carried out in a reactor designed to process multiple substrates simultaneously, e.g., a mini-batch type showerhead reactor.

Various embodiments disclosed herein relate to a semiconductor device, such as a vapor deposition device (e.g., an ALD device, a CVD device, etc.), that includes a manifold for delivering reactant vapor(s) to a reaction chamber. Regardless of the natural state of the chemicals under standard conditions, the reactant vapors may be referred to as “gases” herein. The embodiments disclosed herein can beneficially provide the first reactant and the second reactant through a first supply channel and a second supply channel, respectively, that are offset from each other along a bore of the manifold. The first and second supply channels can supply first and second reactant vapors, respectively, to the manifold. Moreover, the first and second supply channels can also supply purge gas(es) (for example, inert carrier gases) to the manifold to purge the manifold and supply channels of reactant. As explained herein, the offset nature of the first supply channel and second supply channel allows for reduced penetration of the first reactant into the second supply channel and the second reactant into the first supply channel. Penetration of the first reactant into the second supply channel and the second reactant into the second supply channel may cause cross contamination of reactants in the supply channels which can lead to poor deposition quality. Increased offset between the supply channels can reduce penetration of reactants into opposing supply channels.

Further, in various embodiments, the manifold includes an intermediate block surrounded by two valve blocks. Purge gas inlets are provided on surfaces of the valve blocks that are opposite to the surface where the intermediate block and the two valve blocks meet.

FIG. 1 is a perspective view of a semiconductor process device 10 that can include a manifold 100 to deliver gases to a reaction chamber (not shown). The major components of FIG. 1 are described in detail below in connection with the description of FIGS. 4B and 5B. For example, the semiconductor processing device 10 can include a manifold 100 comprising a manifold body 120. First and second valve blocks 110 a, 110 b can be mounted to the manifold body 120 and can include one or a plurality of vapor phase inlets to deliver reactant vapor and/or inactive gas (e.g., purge gas) to the manifold body 120. The semiconductor processing device 10 can include a plurality of valves to control the delivery of reactant vapor and inactive gas to the manifold body 120. For example, as described herein, the device 10 can comprise inert gas valves 132 a, 132 b to control the supply of inactive gas to the manifold 100, reactant gas valves 134 a, 134 b to control the supply of reactant vapor to the manifold 100, and first and second valves 136 a, 136 b to control the supply of etchant and coating vapors to the manifold 100.

In various arrangements, one of the first and second valves 136 a, 136 b can control the flow of etchant(s) from a remote plasma unit (RPU) to periodically clean surfaces of the reaction chamber of deposits (e.g., after every wafer, or after every set number of wafers being processed). The etchant can be activated in the RPU and supplied to the manifold 100 and reaction chamber. In various arrangements, the other of the first and second valves 136 a, 136 b can control the flow of a coating precursor (such as trimethylaluminum, or TMA) which, along with an oxygen source (such as water, remote activated oxygen, ozone, etc.), can be used to periodically coat the chamber with a protective coating (such as aluminum oxide) to deactivate chamber walls, to reduce deposition on the chamber walls, and/or to protect the chamber walls from other chemicals such as etchants.

FIG. 2 is a schematic side sectional view of a semiconductor processing device 20 that can include a manifold 200 to deliver a gas to a reaction chamber (not shown). The semiconductor processing device 20 and manifold 200 shown in FIG. 2 may be generally similar to the semiconductor processing devices and manifolds shown and described in U.S. Pat. No. 9,574,268 and U.S. Patent Publication No. US 2017-0350011, the disclosures of which are incorporated by reference herein in their entirety and for all purposes. There may be various differences between the manifolds described in U.S. Patent Publication No. US 2017-0350011 and the manifold 200 of FIG. 2, but the overall functionality and design may be similar to, e.g., FIGS. 6A-6J and/or FIGS. 8A-8F of U.S. Patent Publication No. US 2017-0350011. Furthermore, the manifold of the present disclosure can be combined with the valves of FIG. 2 of U.S. Patent Publication No. US 2017-0350011; and/or combined with the reactant/inert gas sources, gas dispersion mechanism, controller, reaction chamber and vacuum source of FIG. 3A of the U.S. Patent Publication No. US 2017-0350011.

The manifold 200 can include the manifold body 202 connected with valve blocks 212 a, 212 b, shown on opposite sides of the manifold body 202. Reactant valves and inert gas valves (not shown) are disposed on the blocks 212 a, 212 b, or on other upstream blocks (not shown). An inert gas inlet 220 can supply inert gas to the manifold 200, for example, from an upper portion of the manifold 200. The manifold body 202 comprises multiple blocks stacked on one another to at least partially define a bore 230 along which gas(es) flow, including, for example, an upper block 204, an intermediate block 206, and a lower block 208. In the arrangement of FIG. 2A, the intermediate block 206 comprises a sub-block 206 a and a sub-block 206 b mechanically connected to the sub-block 206 a. The lower block 208 comprises a first sub-block 208 a, a second sub-block 208 b mechanically connected to the first sub-block 208 a, and a third sub-block 208 c mechanically connected to the second sub-block 208 b. The use of multiple blocks and sub-blocks can enable a modular construction of the manifold 200 which can enable the use of internal channels with curved or angled shapes and other internal lumens.

FIG. 2 is a modified version of the manifold described with respect to FIGS. 6A-6J of U.S. Patent Publication No. US 2017-0350011. The sub-blocks 208 a-208 c can define an extended mixing length pathway 280 having a first lateral portion 280 a, an offset axial portion 280 b, and a second lateral portion 280 b. The pathway 280 can provide an extended mixing length downstream of where the supply gases are introduced to the bore 230. The manifold 200 can include a plurality of gas distribution channels, including gas distribution channel 236 shown in FIG. 2A. Supply channels 238 a-c convey gases from the distribution channel 236 to the bore 230. As shown, the supply channels 238 a-c comprise angled supply channels that are angled downwardly to join the bore 230, where the flow is also downward toward an outlet 232. In the arrangement of FIG. 2, gas flows through the bore 230, including along the extended mixing length pathway 280, and exits the manifold 200 through the outlet 232. The outlet 232 can be disposed over a dispersion mechanism, such as a showerhead, which can disperse the gas over the substrate in a reaction chamber (not shown).

Although the arrangement of FIG. 2 can beneficially provide an extended mixing length, the extended mixing length pathway 280 and other pathways in the manifold 200 includes curvature and turns which may introduce dead volumes, for example, during purging of reactant gases. The formation of dead volumes can reduce the efficiency and effectiveness of the deposition process. The curved and angled flow pathways of the arrangement shown in FIG. 2 may also create a “throw” onto the substrate. For example, the use of the curved pathway 280 can impart angular momentum to the gas, which can introduce non-uniformities on the substrate.

Moreover, as shown in FIG. 2, the manifold 200 utilizes a funnel shaped structure as the inactive gas inlet 220 at the top of the bore 230 to introduce purge gas in order to purge the system. However, during injection of the first reactant and/or the second reactant for some processes, the purge gas injected through the inactive gas inlet 220 may not be sufficient, and a dead volume may be present at the top of the bore 230 such that supplied reactant vapor can back-flow into the funnel-shaped inlet 220. The use of o-rings 237 between blocks 204, 206 can further increase the dead volume within the inlet 220. These dead volumes may not be effectively purged from purge gas introduced from the inactive gas inlet 220. Parasitic chemical vapor deposition (CVD) of the reactants along portions of the inlet 220 during injection of the first reactant and/or the second reactant can degrade the performance of the device 20.

FIG. 3A depicts the parasitic deposition of reactant along portions of the inactive gas inlet 220 in the form of a yellow adduct formed within the funnel 220. Further, FIG. 3B shows a block 222 that connects to the top of the funnel 220 which supplies the purge gas into the funnel 220. Yellow adduct indicative of deposited reactant can be seen formed in a first inlet which supplies an inactive gas (e.g., a nitrogen gas, an argon gas, or other inactive gas) to the funnel 220. FIG. 3C shows another side of the block 222 where a second inlet (e.g., an inlet for trimethylaluminium, or TMA) is located. TMA can be supplied to the reactor to form a protective coating on chamber walls, for example, a protective aluminum oxide coating. In some arrangements, the TMA can be applied to the chamber after a set number of cleanings. Yellow adduct can be seen formed in the second inlet which supplies TMA to the system. It can be difficult to remove the illustrated adduct along the inlet 220, which can contaminate the substrate and degrade device quality. Accordingly, there is a need for improved delivery of gases to the reactor.

FIG. 4A shows another schematic side sectional view of the semiconductor processing device 20 which shares all the components of FIG. 2 and therefore will not be discussed again. FIG. 4B is a schematic side sectional view of the semiconductor processing device 10 presented in FIG. 1. The device 10 of FIG. 4B can include a manifold 100 that defines a bore 126 through a manifold body 120. As with FIG. 4A, in some embodiments, the manifold 100 can be constructed by mounting multiple blocks to one another. However, advantageously, in the illustrated embodiment of FIG. 4B, the manifold 100 can be constructed of a single monolithic block which makes up the manifold body 120. A unitary block can improve the manifold body 120 by providing a leak-proof bore 126, for example, by obviating the use of o-rings and/or other interfaces. In various embodiments, deadlegs which can result in contamination may also be avoided. However, alternatively, the manifold body 120 can instead be made of an upper block, an intermediate block, and a lower block as shown in the embodiment of FIGS. 4A and 2. A skilled artisan will recognize multiple blocks and a unitary block are interchangeable based on cost and manufacturing tradeoffs. The use of multiple blocks can enable a modular construction of the module, including curved, angled, or other complex geometries. The bottom of the manifold body 120 can include an outlet 130. First and second valve blocks 110 a, 110 b can also be mounted to the manifold body 120.

The bore 126 of the manifold body 120 can deliver reactant and/or inactive gases to a reaction chamber 30 of a reactor 21 by way of the outlet 130 at the bottom of the manifold body 120. A dispersion device 35, such as a showerhead as shown, or a horizontal injection device in other embodiments, can include a plenum 32 in fluid communication with a plurality of openings 19. The reactant vapor can pass through the openings 19 and be supplied into the reaction chamber 30. A substrate support 22 can be configured, or sized and shaped, to support a substrate 36, such as a wafer, within the reaction chamber 30. The dispersed reactant vapor can contact the substrate and react to form a layer (e.g., a monolayer) on the substrate. The dispersion device 35 can disperse the reactant vapor in a manner so as to form a uniform layer on the substrate.

An exhaust line 23 can be in fluid communication with the reaction chamber 30. A vacuum pump 24 can apply suction to the exhaust line 23 to evacuate vapors and excess materials from the reaction chamber 30. The reactor 21 can comprise any suitable type of semiconductor reactor, such as an atomic layer deposition (ALD) device, a chemical vapor deposition (CVD) device, etc. Moreover, the device 10 can comprise a control system 34 in electronic and data communication with the reactor 21. The control system 34 can comprise one or a plurality of processors configured to control the operation of the device 10. Additional components may be provided to manage the operation of the device 10.

Supply channels 124 a and 124 b can be provided to supply gas from corresponding gas distribution channels to the bore 126. The first supply channel 124 a and the second supply channel 124 b can be in fluid connection with supply channels 122 a and 122 b located in the first valve block 110 a and the second valve block 110 b. The first and second supply channels 124 a, 124 b can merge with the bore 126 at approximately the same region along a longitudinal axis L of the manifold body 120, but inlet openings 127 a, 127 b into the bore 126 can be slightly offset along the longitudinal axis L. As shown in FIG. 4B, the bore 126 can extend continuously along the longitudinal axis L, such that the bore 126 does not include any turns or curved pathways, unlike the arrangement in FIGS. 2 and 4A. An upper end of the bore 126 can be capped by an upper wall 123 that defines a capping surface 128 at the upper end of the bore 126. The first supply channel 124 a can be angled upward towards the capping surface 128 and the second supply channel 124 b can be angled downward towards the outlet 130. Alternatively, the first supply channel 124 a and second supply channel 124 b can be fabricated to be at different levels and arrive at staggered positions at the bore 126. Therefore, the first supply channel 124 a and second supply channel can be angled upwards, downwards, or straight across, and can merge with the bore 126 at offset positions along the longitudinal axis L. In FIG. 4B, the first and second valve blocks 110 a, 110 b can mechanically connect to the manifold body 120 without the use of o-rings. In some embodiments, for example, metal seals can be used between the manifold body 120 and the first and second valve blocks 110 a, 110 b.

The inlet opening 127 a of the first supply channel 124 a can direct gases upwardly into the capping surface 128, which may redirect the supplied gas(es) downwardly through the bore 130. Alternatively, the first supply channel 124 a can terminate well below the capping surface 128. The capping surface 128 can comprise a curved surface shaped so as to efficiently direct the gases impinging on the surface 128 at an angle back down through the bore 126. In FIG. 4B, the capping surface 128 and the outlet 130 can be disposed along the linear longitudinal axis L of the bore 126. Thus, unlike FIG. 4A in which an inert gas inlet 220 is provided in the upper block 204, in the embodiment of FIG. 2B, the uppermost portion of the manifold body 120 is capped, such that the supplied gases, including reactant and inert gases, are provided from the side of the manifold 100.

Beneficially, when the first supply channel 124 a and the second supply channel 124 b meet the bore 126 at a staggered offset position, there is reduced penetration of the first reactant into the second supply channel. An illustration of where the first supply channel 124 a and second supply channel 124 b meet the bore 126 at a staggered offset position is seen in FIG. 7B. In comparison, FIG. 7A illustrates an arrangement where the first supply channel 124 a and the second supply channel 124 b meet the bore 126 at the same position. FIGS. 7A and 7B are described in more detail below. Further, in some embodiments, a first reactant vapor (such as ammonia) can be supplied to the bore 126 along the first supply channel 124 a. A second reactant vapor (such as titanium chloride) can be supplied to the bore 126 along the second supply channel 124 b. As shown in FIG. 4B, the first and second supply channels 124 a, 124 b can be disposed opposite the bore 126 from one another.

If the first and second supply channels 124 a, 124 b are disposed directly across from one another at the same location along the longitudinal axis L, then the first reactant vapor (e.g., ammonia) may be driven into the opposing second supply line 124 b. An example of this effect is illustrated in FIG. 10A and is described in more detail below. Similarly, the second reactant vapor (e.g., titanium chloride) may be driven into the opposing first supply line 124 a. In some arrangements, a low flow of inactive gas may be provided through the first and second supply lines 124 a, 124 b, which can serve as a barrier to reactant vapors from the opposing supply line. However, the reactant vapors may be directed at sufficiently high pressures so as to overcome the low pressure of the inactive gas. Accordingly, in the illustrated embodiment, the inlet openings 127 a, 127 b of the first and second supply channels 124 a, 124 b can be offset from one another along the longitudinal axis L. Moreover, in some embodiments, the inlet openings 127 a, 127 b can be angled opposite to one another along the longitudinal axis L. For example, as shown in FIG. 4B, the upstream first inlet opening 127 a can be angled to have a directional component facing towards the capping surface 128 of the upper wall 123. The downstream second inlet opening 127 b can be angled to have a directional component facing towards the outlet 130. Accordingly, the orientation and/or positioning of the first and second supply channels 124 a, 124 b can reduce or eliminate the penetration of the first reactant into the second supply channel 124 b and the second reactant into the first supply channel 124 a, which can reduce the effects of cross contamination and improve overall deposition quality. An example of this reduced cross contamination is illustrated in FIG. 10B and is described in more detail below.

Moreover, as compared with the arrangement of FIG. 4A, the bore 126 of FIG. 4B can provide improved flow conductance, e.g., higher flow rates, due to the use of a larger diameter bore 126. The larger diameter or major dimension can increase the flow rates of the gas flowing to the reactor 21.

Further, unlike the arrangement of FIG. 4A, purge or inactive gas inlets 108 and 118 can be located at the lateral sides opposite to the side where the valve blocks 110 a/110 b meet the manifold body 120. Thus, unlike the inlet 220 of FIG. 4A, in which inactive purge gas is directed downwardly through a funnel-shaped structure to the bore 230, in the embodiment of FIG. 4B, the inactive purge gas can be directed laterally through supply channels to the bore 126. In some embodiments, the inactive purge gas(es) can be directed through the first and second supply channels 124 a, 124 b through which the first and second reactant vapors are supplied to the bore 126. In other embodiments, the inactive purge gas(es) can be directed through additional supply channels that merge into the bore 126 from a side portion of the bore 126, rather than an upper portion of the bore 126. Beneficially, the embodiment of FIG. 4B can reduce or eliminate dead volumes above the merger point for reactant vapors and the resulting parasitic deposition that can occur in the device 20 of FIG. 4A. Further, the purge or inactive gas inlets 108 and 118 can be located at the last leg of the supply channel so that the whole channel can be directly accessed by the purge gases. Therefore, during the purge cycle, the entire supply channel can be purged which can reduce or eliminate dead volumes.

FIG. 5A shows a top down view of the embodiment of FIGS. 2 and 4A. Each valve block 212 b and 212 a includes gas inlets. The first valve block 212 b includes vapor phase inlet 220 used to input a first gas or vapor phase reactant. The first valve block 212 b also includes vapor phase inlet 222 used to input a low flow rate inactive gas in order to carry vaporized reactant to the reactor 21 and/or to provide a buffer against cross-contamination from other reactants. The second valve block 212 a includes vapor phase inlet 224 used to input a second gas or vapor phase reactant. The second valve block 212 a also includes vapor phase inlet 222 used to supply inactive gas in order to carry vaporized reactant to the reactor 21 and/or to provide a buffer against cross-contamination from other reactants. The manifold body 202 includes the funnel-shaped inlet 220 in which high flow rate inactive gas enters the system in order to purge the device 20. As explained above in connection with FIGS. 2 and 4A, the funnel-shaped inlet 220 can direct the inactive purge gas downwardly into the bore 230. Also, additional etchants (for example, from an RPU) and coating agents (such as TMA) may enter the bore 230 from the funnel-shaped inlet 220. FIG. 5A also illustrates reactant valves 214 a, 214 b mounted to the respective valve blocks 212 a, 212 b. The reactant valves 214 a, 214 b can be used to regulate the flow of the first reactant vapor and the second reactant vapor, respectively.

Examples of inactive gas include argon (Ar) gas or nitrogen (N₂) gas, although any suitable inactive gas may be used. A mix of two different inactive gases can be used. Examples of a first gas phase reactant is a naturally gaseous ALD reactant such as H₂, NH₃, N₂, O₂, or O. The second gas or vapor phase reactant can be produced by a vaporizer (not shown) for vaporizing a reactant which is solid or liquid at room temperature and atmospheric pressure. The vaporizer(s) can comprise, e.g., liquid bubblers or solid sublimation vessels. Examples of solid or liquid reactants that can be held and vaporized in a vaporizer include, without limitation, liquid organometallic precursors such as trimethylaluminum (TMA), TEMAHf, or TEMAZr; liquid semiconductor precursors, such as dichlorosilane (DCS), trichlorosilane (TCS), trisilane, organic silanes, or TiCl₄; and powdered precursors, such as ZrCl₄ or HfCl₄. The skilled artisan will appreciate that embodiments can include any desired combination and arrangement of naturally gaseous, solid or liquid reactant sources. In one implementation, the first reactant vapor comprises NH₃ and the second reactant vapor comprises TiCl₄.

FIG. 5B shows a top down view of the embodiment of FIGS. 1 and 4B. Similar to the first valve block 212 b of FIG. 5A, the first valve block 110 b includes a vapor phase inlet 116 used to supply a first gas or vapor phase reactant and a vapor phase inlet 114 used to supply inactive gas to serve as a carrier or buffer. The first valve block 110 b includes additional vapor phase inlet 112 used to supply an etchant (such as RPU). It is noted that the inlet 112 is disposed on a lateral side of the manifold body 120, e.g., in the valve block 110 b, instead of communicating with the funnel-shaped inlet 220 shown in FIG. 5A. Advantageously, locating the vapor phase inlet 112 at the lateral side of the manifold body leads to a decrease in dead volume which decreases the amount of parasitic deposition. Further, the first valve block 110 b also includes additional inactive vapor phase inlet 118 in which high flow rate inactive gas enters the bore 126 in order to purge the manifold 120. The vapor phase inlet 118 can also be disposed on a lateral side of the manifold body 120, e.g., in the valve block 110 b, instead of communicating with the funnel-shaped inlet 220 shown in FIG. 5A. For example, as shown in FIG. 5B, the inactive vapor phase inlet 118 can be placed on the side opposite to the side in which the first valve block 110 b meets the manifold body 120.

Further, similar to the second valve block 212 a of FIG. 5A, the second valve block 110 a includes a vapor phase inlet 106 used to input a second gas or vapor phase reactant and a vapor phase inlet 104 used to supply low flow rate inactive gas to serve as a carrier or buffer. The second valve block 110 a includes additional vapor phase inlet 102 used to input a coating material (e.g., TMA). It is noted that the inlet 102 can be disposed on a lateral side of the manifold body 120, e.g., in the valve block 110 a, instead of communicating with the funnel-shaped inlet 220 shown in FIG. 5A. Further, the second valve block 110 a also includes additional vapor phase inlet 108 in which high flow rate inactive gas enters the bore 126 in order to purge the manifold 120. The inactive vapor inlet 108 can also be disposed on a lateral side of the manifold body 120, e.g., in the valve block 110 a, instead of communicating with the funnel-shaped inlet 220 shown in FIG. 5A. For example, as shown in FIG. 5B, the inactive vapor phase inlet 108 can be placed on the side opposite to the side where the second valve block 110 a meets the manifold body 120. Similar to FIG. 5A, FIG. 5B illustrates also reactant valves 134 a, 134 b mounted to the respective valve blocks 110 a, 110 b. FIG. 5B further illustrates inactive gas valves 132 a, 132 b and additional first and second valves 136 a, 136 b mounted to the respective valve blocks 110 a/110 b. The inactive gas valves 132 a, 132 b control the inert gas entering from the additional vapor phase inlets 108, 118. Further, as explained above, the first and second valves 136 a, 136 b can control a coating material (e.g., TMA) entering from the vapor phase inlet 102 and an etchant (e.g., an etchant from an RPU) entering from the vapor phase inlet 112, respectively. The description of examples of inert gas, first reactant, and second described above in the description of FIG. 5A is also applicable in FIG. 5B and will not be repeated.

FIGS. 6A and 6B are top cross sectional views of the arrangements of FIGS. 5A and 5B, respectively, showing internal channels within the manifolds. In FIG. 6A, internal channels 220A, 222A, 224A, 226A correspond to internal supply lines that convey the respective vapors from the vapor phase inlets 220, 222, 224, 226, with the reference numerals for the inlets appended by the letter “A” to refer to the corresponding internal supply channel. Similarly, in FIG. 6B, internal channels 102A, 104A, 106A, 108A, 112A, 114A, 116A, 118A correspond to internal supply lines that convey the respective vapors from the corresponding vapor phase inlets 102, 104, 106, 108, 112, 114, 116, 118, with the reference numerals for the inlets appended by the letter “A” to refer to the corresponding internal supply channel. In FIG. 6A, the internal channels are in fluid communication with the reactant valves 214 a, 214 b which regulate the flow of first reactant and second reactant into the reaction chamber. In FIG. 6B, the internal channels are also in fluid communication with the reactant valves 134 a, 134 b which regulate the flow of first reactant and second reactant. Additionally, FIG. 6B illustrates inactive gas valves 132 a, 132 b and the first and second valves 136 a, 136 b as described above. Beneficially, the inactive gases from the inactive gas valves 132 a, 132 b can flow through the entire channel which allows the entire channel to be purged of reactants and yields reduced dead volume.

FIGS. 7A and 7B are perspective views of the interior bores and supply channels for two different arrangements of the first and second supply lines to the bore. FIG. 7B is the offset design shown in FIG. 4B in which a capping surface 128 is disposed at an upper portion of the bore 126 and directs the vapors down the bore 126 through the outlet 130. FIG. 7A also shows a similar design in which a capping surface 506 directs vapors down a bore 502 through an outlet 508. In FIG. 7B, as with FIG. 4B, the supply channels 124 a, 124 b merge with the bore 126 at locations that are offset relative to the longitudinal axis L. In FIG. 7A, by contrast, the supply channels 504 a, 504 b meet at the same position with the bore 126 along the longitudinal axis L. As explained above, the arrangement of FIG. 7B can beneficially reduce cross-contamination of reactants in the supply channels 124 a, 124 b.

FIGS. 8A and 8B shows the velocity plots of the respective bores for the two different supply channel designs of FIGS. 7A and 7B. In FIG. 8B, little or no “throw” is observed, meaning that non-uniformities due to angular momentum of the vapors is reduced. FIGS. 9A and 9B illustrates a NH₃ reactant mole fraction plot of the respective bores for the two different supply channel designs of FIGS. 7A and 7B, respectively. The non-uniformity displayed in FIG. 9A is lower than the non-uniformity displayed in FIG. 9B. Further, note that non-uniformity of the bore in the design of FIGS. 2, 4A, 5A, and 6A is significantly lower than the non-uniformity displayed in FIGS. 9A and 9B. While non-uniformity during mixed deposition of two reactants may be higher in the design of FIGS. 7A and 7B (and 4B) as compared with that of FIG. 4A, in some embodiments it may be more important to provide high flow rate or conductance pulses, for example, to achieve high aspect ratio structures. In such processes, mixing non-uniformity may be less important than high flow conductance, and the design of FIG. 4B may be preferred.

FIGS. 10A and 10B illustrates the mole fraction of NH₃ reactant the position within the supply channels and the bore, respectively, for the two different supply channel designs of FIGS. 7A and 7B. Region C to the left of the vertical extending yellow highlighted region depicts a position within the first supply channel which inputs NH₃ reactant. The NH₃ level is high in both the different supply channel designs within Region C. Region A within the vertical extending yellow highlighted region depicts the bore region. Comparing the right edge portion of Region A for FIGS. 10A and 10B, the NH₃ level tapers off much faster in the offset design depicted in FIG. 7B than the straight T design of FIG. 7A. Region B to the right of the vertical extending yellow highlighted region depicts a region within the second supply line. The left edge portion of Region B displaying where the bore meets the second supply line shows high concentrations of NH₃ in FIG. 10A and comparatively low concentrations of NH₃ in the same region in FIG. 10B depicting remarkably less penetration of NH₃ into the second supply line for the offset design of FIG. 7B. Therefore, there is less unwanted penetration of NH₃ into the second supply line in the offset design of FIG. 7B.

Although the foregoing has been described in detail by way of illustrations and examples for purposes of clarity and understanding, it is apparent to those skilled in the art that certain changes and modifications may be practiced. Therefore, the description and examples should not be construed as limiting the scope of the invention to the specific embodiments and examples described herein, but rather to also cover all modification and alternatives coming with the true scope and spirit of the invention. Moreover, not all of the features, aspects and advantages described herein above are necessarily required to practice the present invention. 

What is claimed is:
 1. A semiconductor processing device comprising: a manifold comprising: a bore configured to deliver vaporized reactant to a reaction chamber, the bore extending along a longitudinal axis; an upper wall disposed at an upper portion of the manifold, the upper wall defining a capping surface at a first end of the bore along the longitudinal axis; an outlet at a lower portion of the manifold along the longitudinal axis, the outlet configured to deliver gas to a reactor; a first supply channel configured to supply gas to the bore; and a second supply channel configured to supply gas to the bore, wherein the first supply channel and the second supply channel merge with the bore at offset positions along the longitudinal axis.
 2. The semiconductor processing device of claim 1, wherein the capping surface is shaped to redirect upwardly directed gas downwardly back through the bore to the outlet.
 3. The semiconductor processing device of claim 1, further comprising a first block mounted to the manifold, the first block and the manifold cooperating to at least partially define the first supply channel.
 4. The semiconductor processing device of claim 3, further comprising a second block mounted to the manifold, the second block and the manifold cooperating to at least partially define the second supply channel.
 5. The semiconductor processing device of claim 1, wherein the first supply channel is in fluid communication with a first reactant source and is configured to deliver a first vaporized reactant to the bore, and wherein the second supply channel is in fluid communication with a second reactant source and is configured to deliver a second vaporized reactant to the bore.
 6. The semiconductor processing device of claim 1, wherein the first supply channel is in fluid communication with an inactive gas to purge the bore.
 7. The semiconductor processing device of claim 1, further comprising a showerhead device below the outlet, the showerhead device configured to disperse a flow of the gas from the outlet.
 8. The semiconductor processing device of claim 7, further comprising a reaction chamber below the showerhead device and a substrate support configured to support a substrate in the reaction chamber.
 9. The semiconductor processing device of claim 3, wherein the first block comprises a first vapor phase inlet configured to input a first reactant into the first supply channel.
 10. The semiconductor processing device of claim 9, wherein the first block further comprises a second vapor phase inlet and a third vapor phase inlet.
 11. The semiconductor processing device of claim 10, wherein the first block further comprises a fourth vapor phase inlet, wherein the fourth vapor phase inlet is located on a lateral side of the first block opposite to the manifold.
 12. The semiconductor processing device of claim 11, wherein the fourth vapor phase inlet is configured to input a purge gas into the manifold.
 13. The semiconductor processing device of claim 1, wherein the first supply channel is angled towards the capping surface and the second supply channel is angled towards the outlet, the second supply channel downstream of the first supply channel.
 14. The semiconductor processing device of claim 1, wherein the manifold comprises a single monolithic block.
 15. The semiconductor processing device of claim 1, wherein the bore extends continuously along the longitudinal axis.
 16. A semiconductor processing device comprising: a manifold comprising a bore configured to deliver gas to a reaction chamber, the bore disposed along a longitudinal axis; an upper wall disposed at an upper portion of the manifold, the upper wall defining a capping surface at a first end of the bore along the longitudinal axis; a first supply line configured to supply an inactive purge gas to the bore at a first location along the longitudinal axis downstream of the capping surface; a second supply line configured to supply a gas to the bore at a second location along the longitudinal axis, the second location different from the first location.
 17. The semiconductor processing device of claim 16, wherein the supply line is connected to an inactive gas source to purge the bore.
 18. The semiconductor processing device of claim 16, wherein the inactive gas comprises at least one of argon gas and nitrogen gas.
 19. A method of deposition, the method comprising: supplying a first gas through a first supply channel to a bore of a manifold at a first location along a longitudinal axis of the bore, a capping surface disposed at an upper end of the bore; supplying a second gas through a second supply channel to the bore of the manifold at a second location along the longitudinal axis of the bore that is longitudinally offset from the first supply channel; directing at least one of the first gas and the second gas downstream along the longitudinal axis towards an outlet of the bore.
 20. The method of claim 19, wherein supplying the first and second gases comprises supplying a first vaporized reactant and supplying a second vaporized reactant.
 21. The method of claim 20, further comprising purging the reaction chamber with an inactive gas after supplying the first vaporized reactant and before supplying the second vaporized reactant.
 22. The method of claim 21, wherein the inactive gas comprises at least one of nitrogen gas and argon gas.
 23. The method of claim 22, wherein the first vaporized reactant comprises at least one of H₂, NH₃, N₂, O₂, or O.
 24. The method of claim 23, wherein the second vaporized reactant comprises at least one of dichlorosilane (DCS), trichlorosilane (TCS), trisilane, organic silanes, titanium chloride (TiCl₄), ZrCl₄, and HfCl₄.
 25. The method of claim 24, wherein the first vaporized reactant comprises NH₃ and the second vaporized reactant comprises TiCl₄.
 26. The method of claim 25, further comprising vaporizing liquid TiCl₄ to create the second vaporized reactant. 